Crosslinkable surface coatings

ABSTRACT

A novel aqueous polymeric formulation is disclosed. Also disclosed are methods of making the polymeric formulation, and of using the polymeric formulation to produce a crosslinked polymeric surface coating on a substrate. One embodiment of the novel polymeric formulation comprises an aqueous carrier; at least one polymeric-ingredient; a non-polymeric polyfunctional amine; and base. The one polymeric ingredient has both acid-functional and acetoacetoxy-type functional pendant moieties. The non-polymeric polyfunctional amine has at least two amine-functional moieties. The amount of base contained within the formulation is effective for inhibiting gellation, which would otherwise occur as a result of crosslinking between the acetoacetoxy-type functional and amine-functional moieties. Another embodiment of the novel polymeric formulation comprises at least two polymeric ingredients, one of which has acetoacetoxy-type functional pendant moieties and the other of which has acid-functional pendant moieties.

This is a divisional of application Ser. No. 08/320,795, filed on Oct.7, 1994 now U.S. Pat. No. 5,498,659 which is a continuation of Ser. No.07/833,250 filed on Feb. 10, 1992 abandoned.

TECHNICAL FIELD

The present invention is generally directed to novel polymericcompositions-of-matter that are able to provide various substrates withcrosslinked polymeric surface coatings and films at room temperature.Such compositions-of-matter, for example, may take the form of asolution, a dispersion, an emulsion, or a formulation, as dictated by aparticular "end-use" requirement or other consideration.

In that regard, one particularly noteworthy aspect or feature of thepresent invention is directed to a formulation that is characterized asa storage-stable single-package novel polymeric composition-of-matterthat contains at least one polymeric ingredient. Additional embodimentsof the composition-of-matter of the present invention contain two ormore polymeric ingredients. In the case where there is only onepolymeric ingredient, such polymeric ingredient has both acid-functionalas well as acetoacetoxy-type functional pendant moieties; and in thecase where there are two or more such polymeric ingredients, one hasonly acid-functional pendant moieties and the other has onlyacetoacetoxy-type functional pendant moieties.

Yet another ingredient of the novel formulation or composition-of-matteris a "non-polymeric" polyfunctional amine having at least twoamine-functional moieties.

The composition-of-matter or formulation of the present inventionfurther includes "base", in an amount that is effective for providingstorage stability.

The formulation or composition-of-matter additionally includes certainvolatile, "carrier" ingredients that are able to evaporate at roomtemperature.

Still another aspect or feature of the present invention is directed tonovel methods of producing the novel polymeric compositions-of-matter,briefly mentioned above.

Yet another aspect or feature of the present invention is directed to amethod of applying the novel polymeric compositions-of-matter orformulations onto a substrate, for purposes of producing a crosslinkedpolymeric surface coating on the substrate at room temperature.

BACKGROUND ART

In February of 1988, F. Del Rector et al. (three authors in total)presented in New Orleans, La., United States of America, a technicalpaper entitled "Applications For The Acetoacetyl Functionality InThermoset Coatings".

Briefly stated, these three authors reviewed some of the many,then-known methods and/or procedures for incorporating certain so-called"activated methylene" groups into different types or classes of resins,for purposes of preparing certain polymeric thermoset surface coatingsand films, via a number of then-known crosslinking mechanisms.

More particularly, these authors discussed various well-known methodsfor reacting certain acetoacetyl-functional moiety-containing polymerswith certain melamines, with certain isocyanates, with certainaldehydes, with certain diamines, and with certain other specifiedreactants via the so-called "Michael" reaction, to achieve desiredcrosslinking of the acetoacetyl-functional moiety.

For example, European Patent Application 0 326 723/A1 (assigned to Rohm& Haas Co.) discloses one such well-known method for producing aconventional "two-package" polymeric surface-coating composition that issaid to be able to "cure" at ambient conditions. In particular, when thecontents of the two packages constituting the composition are combined,the composition is said to consist of a tertiary amine ingredient, asecond ingredient characterized as an epoxide ingredient, a thirdingredient characterized as an acetoacetoxy ingredient, and a fourthingredient that is said to possess Michael-reactive double bonds.

U.S. Pat. No. 4,408,018 (to Bartman et al.) notes that the reaction ofacetoacetic ester with acrylic acid ester in the presence of a strongbase is illustrative of the Michael reaction. Bartman et al. furthernote that certain "enols" as well as certain "enolates" are known to addacross the double bonds of certain alpha, beta-unsaturated ketones andesters. In general, the '018 Bartman patent is directed to crosslinkingacetoacetate-type moiety-containing monomer (via the noted Michaelreaction) with certain alpha, beta-unsaturated esters. In particular,when tetrabutyl ammonium hydroxide is used as "base", as is disclosed inthe '018 Bartman patent, a composition containing the above-discussed,known, mutually-reactive ingredients is said to gel in three (3) hoursor less.

Indeed, well-known two-package polymeric surface-coating compositions(or formulations) containing the above-mentioned mutually-reactiveingredients typically gel rapidly, after the mutually-reactiveingredients are combined; and such a "rapid-gelling" characteristicoftentimes renders such known compositions either inappropriate forvarious applications or simply undesirable. For example, the use oftwo-package polymeric surface coatings of this sort may give rise to"waste"; and, because of such generation of waste, such two-packagecompositions may therefore be environmentally less desirable than asingle-package composition.

U.S. Pat. No. 3,668,183 to Hoy et al. discloses single-package polymericsurface-coating compositions that include a "blocked" polyamineingredient as well as a polyacetoacetate or a polyacetoacetamideingredient that is mutually-reactive with the polyamine. (A ketone oraldehyde is utilized as the "blocking" agent, for the polyamineingredient.) The various single-package polymeric compositions disclosedin the '183 Hoy patent are typically diluted with conventional solvents.Illustrative solvents include an assortment of commercially-availablesolvents, wherein such are often characterized as volatile organiccompounds ("VOCs"). Typically, water is not included as such a solvent,in the formulation of single-package polymeric compositions. Indeed, asdisclosed in the '183 Hoy patent, such single-package polymericcompositions are characterized as being relatively stable, only in theabsence of water.

Furthermore, U.S. Pat. No. 4,772,680 (to Noomen et al.) points out thatthe coating compositions disclosed in U.S. Pat. No. 3,668,183 to Hoy etal. (discussed above) are known to possess certain undesirableproperties. For example, Noomen et al. note that the coatingcompositions of the '183 Hoy patent are known to display certain"unsatisfactory" properties, both to water as well as to certain acids,and unsatisfactory "weathering" properties, when subjected to certainoutdoor-exposure conditions.

To distinguish their invention from the '183 Hoy patent, Noomen et al.point out (in the '680 patent) that their invention is based upon liquidcoating compositions that include a polyacetoacetate ingredient and ablocked polyamine ingredient which is said to be "different" from theblocked polyamine ingredient that is disclosed in the '183 Hoy patent.In particular, the amino groups of the polyamine ingredient disclosed inthe '680 Noomen patent are said to be blocked by an aldehyde or ketoneof specified structure; and water is identified as a "suitable" solvent.However, when Noomen et al., in their number of examples, preparevarious coating compositions by combining the mutually-reactivepolyacetoacetate-containing and "blocked" polyamine-containingingredients, such compositions are shown to "gel" in 3 hours or less,which is impractical for a number of surface-coating applications.

Thus, a practical single-package polymer-based coating composition,containing the two above-discussed mutually-reactiveingredients--namely, an acetoacetate-type moiety-containing ingredientand an amine moiety-containing ingredient--has not heretofore been ableto be made. Yet, a practical, commercially-available single-packagecoating composition containing these two particular mutually-reactiveingredients is presently in great demand.

For example, European Patent Application 0 341 886/A2 (assigned to ICIResins BV) discloses an aqueous coating composition that ischaracterized as a polymer "system" which is said to include a vinylpolymer having chain-pendant amine-functional groups as well aschain-pendant carbonyl-functional groups. Alternatively, the polymersystem may include a vinyl polymer bearing a chain-pendantamine-functional group and another polymer molecule bearing achain-pendant carbonyl-functional group.

Such a coating composition is said to be able to undergo a so-called"self crosslinking" reaction during and/or after coating formation.

It is thought that the "self crosslinking" reaction occurs via theformation of azomethine groups. Chain-pendant amine functionality issaid to be preferably introduced into the vinyl polymer via an"imination" reaction, which in turn is said to preferably involvecarboxyl (or carboxylate salt) groups of a precursor polymer and anaziridine compound.

Particularly preferred vinyl polymers, which are said to include pendantpolymerized units having amine-functional groups as well as pendantpolymerized units derived from olefinically-unsaturated monomer, includepolymerized units derived from acetoacetoxyethyl methacrylate. Examples2 and 9 each describe the preparation of an aqueous-based coatingcomposition that was used to produce a film on glass plates. There is,however, no disclosure or even a suggestion in European PatentApplication 0 341 886/A2 that these aqueous-based coating compositionspossess any storage stability over an extended period of time.

Another example of an aqueous coating composition is disclosed inEuropean Patent Application 0 390 370/A1 (assigned to Imperial ChemicalIndustries PLC and ICI Resins BV). In particular, European PatentApplication 0 390 370/A1 discloses a coating composition--alsocharacterized as "self crosslinkable"--that is said to include at leastone polymer having chain-pendant amine-functional groups as well as atleast one so-called "non-polymeric" compound having at least two ketonegroups that are reactable with the chain-pendant amine groups.

It is thought that the "self crosslinking" reaction occurs via theformation of enamine groups, via elimination of water.

While European Patent Application 0 390 370/A1 discloses that theseaqueous-based coating compositions seem to possess 5 weeks storagestability, there is no disclosure or even a suggestion in EuropeanPatent Application 0 390 370/A1 that these aqueous-based coatingcompositions possess any storage stability for an extended period oftime such as one (1) year or more.

It is, therefore, clearly presently desirable that there be commerciallyavailable a single-package polymeric surface coating compositioncontaining the above-discussed mutually-reactive acetoacetoxy-typefunctional and amine-functional ingredients. It would further bedesirable that such a coating composition be stable over an extendedperiod of time such as 12 months or even longer at room temperature,prior to use.

Moreover, because of the present desire to reduce the total amount ofindustrial solvents known as volatile organic compounds ("VOCs"), inboth consumer and various industrial compositions and formulations, itwould be even more desirable that such a single-package composition bewater-based as well.

SUMMARY DISCLOSURE OF INVENTION

As was briefly mentioned above, one aspect or feature of the presentinvention is directed to a storage-stable single-package novel polymericcomposition-of-matter or formulation that contains at least onepolymeric ingredient. Additional embodiments of thecomposition-of-matter of the present invention contain two or morepolymeric ingredients. In the case where there is only one polymericingredient, such polymeric ingredient has both acid-functional as wellas acetoacetoxy-type functional pendant moieties; and in the case wherethere are two or more such polymeric ingredients, one has onlyacid-functional pendant moieties and the other has onlyacetoacetoxy-type functional pendant moieties.

Still another ingredient of the composition-of-matter or formulation isa so-called "non-polymeric" polyfunctional amine-containing compoundhaving at least two amine-functional moieties.

Optional additional ingredients include polymeric thickeners, polymericflow-modifying ingredients, and various dispersion or emulsion polymersas well as various solution polymers.

The composition-of-matter or formulation of the present inventionfurther includes "base", in an amount that is effective for providingstorage stability.

The composition-of-matter or formulation additionally includes anevaporable carrier. The evaporable carrier may consist essentially ofwater only, or may comprise water and at least one additional volatileliquid that is able to evaporate at room temperature, wherein the totalamount of volatile organic compounds ("VOCs") in the formulation doesnot exceed 200 grams per liter of the formulation.

The novel polymeric composition-of-matter of the present invention isthus a water-based, "single-package" polymeric composition. Moreover,until used, the novel single-package water-based composition of thepresent invention will remain stable for 12 months or more, when storedat ambient or room temperature. Still further, the single-packagewater-based polymeric composition of the present invention possesses"improved" storage stability, in comparison to conventionalsingle-package compositions, when stored at elevated temperature such as35 degrees Celsius to 55° C. over extended periods of time.

To use, the aqueous polymeric composition-of-matter of the invention issimply applied to a suitable substrate.

Suitable substrates include cardboard, paper, wood, linoleum, concrete,stone, marble and terrazzo, and a variety of metal surfaces includingpolished metal surfaces and metal foils.

Evaporation (from the substrate) of the volatile components oringredients of the aqueous polymeric composition, at room temperature orat elevated temperature, in turn enables the acetoacetoxy-typefunctional moieties contained within the composition to desirablycrosslink with the amine-functional moieties (also contained within thecomposition), thereby producing a crosslinked polymeric coating on thesubstrate.

These and other features and advantages of the present invention will bediscussed in greater detail hereinbelow.

INDUSTRIAL APPLICABILITY

The novel, aqueous polymeric compositions-of-matter or formulations ofthe present invention can be utilized, in general, to produce suchsurface coatings as floor polishes, paints, adhesives and so forth, ormore particularly, to produce durable, abrasion-resistant andsolvent-resistant surface coatings or "finishes" on various substratessuch as cardboard, concrete, counter tops, floors, marble and terrazzo,paper, stone, tile, wood and a variety of metal surfaces includingpolished metal surfaces and metal foils.

Still another application for the aqueous polymericcomposition-of-matter or formulation of the present invention is in theproduction of water-based adhesives for various consumer and industrialuses.

Industrial end-use applications include surface-coatings and "finishes"for construction machinery and equipment, for bridges and road surfaces,for various parts or components of certain production-line machinery,and for a wide assortment of automotive components.

Consumer end-use applications include durable polymeric films andsurface coatings for Various components of such a wide assortment ofhome-use appliances as clothes washers and dryers, dishwashers, radios,ranges and ovens, refrigerators, television sets, and video cassetterecorders ("VCRs").

End-use applications for wood--industrial use, home use, andotherwise--include but are not limited to interior and exterior woodsurface coatings such as stains and varnishes.

The novel aqueous polymeric compositions-of-matter or formulations ofthe present invention can also be used by industry or consumers asthickeners for paints and other surface coatings, as well as thickenersfor printing inks and other formulations which need to "crosslink" upondrying. Further in that regard, various specific aqueous polymericformulations produced in accordance with the principles of the presentinvention are able to provide certain "finishes" as well as othersurface "treatments" for a number of relatively thin substrates such aspaper, wherein such "finishes" and surface "treatments" are able tocrosslink without liberating formaldehyde. Such an end-use isparticularly desirable, for example, in the production of "release"coatings, overprint varnishes, and especially in relation to theproduction of rotogravure coatings.

Yet another specific end-use for the aqueous polymericcomposition-of-matter or formulation of the present invention is in theproduction of a wide assortment of architectural surface coatings whichneed to form films of various thicknesses, at relatively lowtemperatures--that is, from about 25 degrees Celsius to about zerodegrees Celsius--yet which provide desirable "surface hardness" and"durability" qualities, due to their crosslinked polymeric structure.

The novel aqueous polymeric composition-of-matter or formulation of thepresent invention can, moreover, be shipped in bulk-sized quantities orin various smaller-sized containers, as desired. For example, to satisfycertain industrial users, the aqueous polymeric composition-of-matter orformulation of the present invention can readily be shipped in 55-gallondrums, or in larger quantities such as in rail cars, if desired. Yet, ifconsumers desire smaller, more conveniently-sized volumetric quantities,the aqueous polymeric compositions can be sold in 1-gallon (or smaller)containers or even in conventional aerosol containers, as desired and aspermitted by governmental authority.

BEST MODE FOR CARRYING OUT THE INVENTION

While the present invention is susceptible to embodiment in variousforms, there is hereinbelow described in detail several presentlypreferred embodiments, with the understanding that the presentdisclosure is to be considered as merely an exemplification of thepresent invention, without limitation to the specific embodiments orexamples discussed.

In the ensuing detailed description, certain terms as well as certainterminology (generally known by those skilled in the art) will beutilized for purposes of conciseness, and for otherwise elucidating thefeatures and advantages of the present invention. Such terms are eitherdefined as follows or are otherwise intended to mean the following.

The term "dispersion" is understood to connote a two-phase system ofwhich one phase consists of finely-divided particles, often in thecolloidal-size range, distributed throughout a "bulk" substance, whereinsuch finely-divided particles provide the "disperse" or internal phaseand the bulk substance provides the "continuous" or external phase.

The term "elevated temperature" as used herein means any temperaturegreater than room temperature.

The term "emulsion" is understood by those skilled in the art asinvolving a stable mixture of two or more immiscible liquids held insuspension by small percentages of substances called "emulsifiers" (alsocalled "surfactants" or "soaps"). All emulsions are known to includeboth a continuous phase as well as a discontinuous phase that isdispersed throughout the continuous phase.

The term "emulsion polymerization" is understood by those skilled in theart as involving the polymerization of monomers in aqueous media to formdispersed polymers having particle diameters in the range ofapproximately 20 to 1000 nm. (10⁹ nanometers ("nm") are equivalent toone meter).

The term "glass-transition temperature" is understood by those skilledin the polymer chemistry art as representing the temperature at whichthe amorphous domains of a polymer take on the characteristic propertiesof the "glassy" state, wherein such polymeric glassy-state propertiesinclude brittleness, stiffness and rigidity.

The term "latex" is understood to refer to the product of a particularemulsion-polymerization reaction. In that regard, the term "latex" istypically understood to mean an "aqueous" or water-based polymeremulsion, without separation of the polymer product from the water andthe other components that are contained within the emulsion.

The term "pendant moiety", in conjunction with chemical structure, isunderstood to mean a moiety which is attached to the backbone of apolymer molecule. Certain pendant moieties may be used for crosslinkingpurposes. Moreover, the term "pendant moiety" as used herein includesend groups.

The term "room temperature" shall be understood to mean a temperature offrom about 20 degrees Celsius to about 25 degrees Celsius.

A number of additional terms are defined further below, throughout thebody of this patent specification.

As was briefly mentioned above, one particularly noteworthy aspect orfeature of the water-based polymeric composition-of-matter orformulation of the present invention, is the fact that it is asingle-package composition which will remain stable for 12 months ormore when stored at room temperature. Also, as was briefly mentionedabove, the present invention is directed to a novel, low-VOC,water-based composition-of-matter or formulation that may contain onlyone polymeric ingredient or that may contain at least two polymericingredients. In the former case, the polymeric ingredient possesses bothacid-functional as well as acetoacetoxy-type functional pendantmoieties; and in the latter case, one polymeric ingredient has onlyacid-functional pendant moieties and the other polymeric ingredient hasonly acetoacetoxy-type functional pendant moieties. In the former case,the polymeric ingredient contains acid functionality sufficient toprovide the polymeric ingredient with an acid number in the range ofabout 30 to about 300; and the weight-average molecular weight ("Mw")value of such a polymeric ingredient is typically between about 2,000and 50,000. In this regard, the term "acid number" indicates the numberof milligrams ("mg") of potassium hydroxide ("KOH") required toneutralize one gram of the polymeric ingredient.

Furthermore, the polymeric ingredient, in the former case, preferablyhas an acid number in the range of about 50 to about 150. Also, thepolymeric ingredient, again in the former case, preferably has an Mwvalue of about 2,000 to about 40,000 and more preferably of about 2,000to about 30,000.

However, in the latter case, there are at least two different polymericingredients and the polymeric ingredient having only acetoacetoxy-typefunctional pendant moieties typically has an Mw value of about 2,000 toabout 1,000,000. Preferably, the Mw value is between about 5,000 andabout 500,000; more preferably, the Mw value is between about 15,000 andabout 300,000; and most preferably, the Mw value is between about 50,000and about 200,000.

Also, with respect to the latter case, the polymeric ingredientpossessing only acid functionality, which resembles the polymericingredient of the former case, particularly with respect to acid numberranges, may only be polymeric in structure. In particular, such apolymeric ingredient also preferably has an acid number in the range ofabout 50 to about 150 as well as an Mw value of preferably about 2,000to about 40,000, more preferably about 2,000 to about 30,000.

The "non-polymeric" polyfunctional amine-containing compound (possessingat least two amine-functional moieties) typically has a chemical-formulaweight of less than about 2,000 grams per mole, and preferably has achemical-formula weight of less than about 1,000. grams per mole.

Another aspect or feature of the present invention is the method bywhich the aqueous polymeric composition-of-matter is produced. Stillanother aspect or feature of the present invention is the method wherebythe aqueous polymeric composition-of-matter is applied to a suitablesubstrate to produce a crosslinked polymeric surface coating or film onthe substrate.

One step of a particularly preferred method of producing the aqueouspolymeric composition-of-matter is to combine preselected relativeamounts of initiator, "surfactant" (also called "soap" or "emulsifier")and evaporable aqueous carrier in an agitated reactor of suitable size,and to heat the agitated reactor contents to a desired reactiontemperature, typically 40 to 90 degrees Celsius, more preferably 75 to85 degrees Celsius, over a predetermined period of time, which maytypically be 1 hour. At least one chain-transfer agent, which isoptional, may also be incorporated into the agitated reactor contents atthis time, if desired. Nitrogen or another suitable "inert" gas may beintroduced into the reactor headspace to eliminate oxygen from thereaction vessel, if desired.

The surfactant ingredient (or surfactant ingredients, if several areused) typically comprises at least one non-ionic emulsifier, at leastone anionic emulsifier, or a mixture of non-ionic and anionicemulsifiers. Cationic emulsifiers as well as amphoteric emulsifier's mayalso be used in certain situations if desired.

Examples of useful anionic surfactants include but are not limited toorganosulfates and sulfonates, for example, sodium and potassium alkyl,aryl and alkaryl sulfates and sulfonates, such as sodium 2-ethyl hexylsulfate, potassium 2-ethyl hexyl sulfate, sodium nonyl sulfate, sodiumlauryl sulfate ("NaLS"), potassium methylbenzene sulfonate, potassiumtoluene sulfonate, and sodium xylene sulfonate; so-called "higher" fattyalcohols, for example, stearyl alcohols, lauryl alcohols, and so forth,which have been ethoxylated and sulfonated; dialkyl esters of alkalimetal sulfosuccinic acid salts, such as sodium or potassium diamylsulfosuccinates, in particular sodium dioctyl sulfosuccinate; variousformaldehyde-naphthalene sulfonic acid condensation products; alkalimetal salts, as well as so-called "partial" alkali metal salts, and freeacids of complex organic phosphate esters; and combinations thereof.

Examples of non-ionic surfactants which can be used in this inventioninclude but are not limited to polyethers, for example, ethylene oxideand propylene oxide condensates which include straight and/or branchedchain alkyl and alkaryl polyethylene glycol and polypropylene glycolethers and thioethers; alkyl-phenoxy poly(ethyleneoxy) ethanols havingalkyl groups containing from about 7 to about 18 carbon atoms and havingfrom about 4 to about 240 ethyleneoxy units, such as heptyl-phenoxypoly(ethyleneoxy) ethanols, nonyl-phenoxy poly(ethyleneoxy) ethanols,and so forth; the polyoxyalkylene derivatives of hexitol, includingsorbitans, sorbides, mannitans, and mannides; partial so-called "long"chain fatty-acid esters, such as the polyoxyalkylene derivatives ofsorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate,sorbitan tristearate, sorbitan monooleate, and sorbitan trioleate; thecondensates of ethylene oxide with a hydrophobic base, such as a basethat is formed by condensing propylene oxide with propylene glycol;sulfur-containing condensates, for example, those prepared by condensingethylene oxide with higher alkyl mercaptans, such as nonyl, dodecyl, ortetradecyl mercaptan, or with alkyl thiophenols wherein the alkyl groupcontains from about 6 to about 15 carbon atoms; ethylene oxidederivatives of long-chain carboxylic acids, such as lauric, myristic,palmitic, or oleic acids or mixtures of acids, such as so-called "tall"oil fatty acids; ethylene oxide derivatives of long chain-alcohols suchas octyl, decyl, lauryl, or cetyl alcohols; and combinations thereof.

In the preparation of certain preferred embodiments of the aqueouspolymeric compositions or formulations of the invention, the evaporablecarrier will consist essentially of water ("H₂ O") only. However, in thepreparation of certain other embodiments of the aqueous polymericcompositions or formulations of the invention, it will be desirable thatthe evaporable carrier comprise water and at least one otherwater-miscible volatile organic liquid, wherein the amount of volatileorganic compounds ("VOCs") does not exceed 200 grams per liter of theformulation.

Examples of water-miscible volatile organic liquids that are useful inthis regard include but are not limited to alcohols; dialkyl ethers;ethylene and propylene glycols and their monoalkyl and dialkyl ethers;relatively low formula weight polyethylene oxides and their alkyl anddialkyl ethers (i.e., having a chemical-formula weight of less thanabout 200 grams per mole); dimethyl formamide; dimethyl acetamide; andcombinations thereof.

After the desired reaction temperature is achieved, anemulsion-polymerizable mixture is incorporated into the agitated reactorcontents over a predetermined period of time, such as 1 hour, whilemaintaining the desired reaction temperature.

One embodiment of such an emulsion-polymerizable mixture may include amonomeric ingredient having acid-functionality; and another embodimentof the emulsion-polymerizable mixture may include at least oneacetoacetoxy-type functional moiety-containing monomeric ingredient aswell as at least one acid moiety-containing monomeric ingredient. Ineither case, the acid moiety-containing ingredient is typicallyethylenically-unsaturated.

The emulsion-polymerizable mixture may optionally further include atleast one monomeric or polymeric acrylic or methacrylic acid ester aswell as at least one polymeric or monomeric alkene (such as ethylene) orat least one vinylic monomer or polymer, provided that any suchadditional (optional) ingredient is addition-polymerizable with theacetoacetoxy-type functional moiety-containing and acidmoiety-containing ingredients briefly mentioned above.

Examples of suitable acrylic and methacrylic acid esters include but arenot limited to methyl acrylate ("MA"), methyl methacrylate ("MMA"),ethyl acrylate, ethyl methacrylate, propyl acrylate, propylmethacrylate, butyl acrylate ("BA"), butyl methacrylate, 2-ethyl hexylacrylate ("2-EHA"), 2-ethyl hexyl methacrylate, decyl acrylate, decylmethacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate ("HEMA"),hydroxypropyl acrylate, hydroxypropyl methacrylate, and combinationsthereof.

Suitable vinyl monomers include but are not limited to acrylamide;acrylonitrile; 1,2-butadiene; 1,3-butadiene; chloroprene;1,3,5-hexatriene; styrene ("St"); alpha-methyl styrene; vinyl acetate;vinyl chloride; vinyl toluene; vinylidene chloride; and combinationsthereof.

Acetoacetoxy-type functional moiety-containing ingredient, suitable forpurposes of the present invention, are monomers having the ability toform stable enamine structures by reaction with amines, and having thefollowing structure: ##STR1## wherein R₁ is either H, alkyl (i.e., C₁ toC₁₀), or phenyl; wherein A is either: ##STR2## wherein R₂ is either H,alkyl (i.e., C₁ to C₁₀), phenyl, subsituted phenyl, halo, CO₂ CH₃, orCN;

wherein R₃ is either H, alkyl (i.e., C₁ to C₁₀), phenyl, substitutedphenyl, or halo;

wherein R₄ is either alkylene (i.e., C₁ to C₁₀), phenylene, orsubstituted phenylene;

wherein R₅ is either alkylene or substituted alkylene;

wherein any of "a", "m", "n", and "q" is either 0 or 1;

wherein each of "X" and "Y" is either --NH-- or --O--;

and wherein "B" is either "A", alkyl (i.e. C₁ to C₁₀), phenyl,substituted phenyl, or heterocyclic.

Preferred ethylenically-unsaturated acetoacetoxy-type functionalmoiety-containing ingredients include, among the following, variousacetoacetamides, including but not limited to: ##STR3##acetoacetoxyethyl methacrylate ("AAEM"); acetoacetoxyethyl acrylate("AAEA"); allyl acetoacetate; vinyl acetoacetate; and combinationsthereof.

AAEM is structurally represented as: ##STR4## AAEA is structurallyrepresented as: ##STR5## allyl acetoacetate is structurally representedas: ##STR6## and vinyl acetoacetate is structurally represented as:##STR7##

Particularly preferred ethylenically-unsaturated acetoacetoxy-typefunctional moiety-containing ingredients are acetoacetoxyethylmethacrylate ("AAEM"), acetoacetoxyethyl acrylate ("AAEA"), andcombinations thereof.

Ethylenically-unsaturated carboxylic acid moiety-containing monomerssuitable for purposes of the invention include but are not limited toacrylic acid, ethacrylic acid, fumaric acid-monoethyl ester, fumaricacid, itaconic acid, maleic acid, maleic anhydride, methacrylic acid("MAA"), fumaric acid-monomethyl ester, methyl hydrogen maleate, andcombinations thereof.

Ethacrylic acid is structurally represented as ##STR8##

Fumaric acid-monoethyl ester is structurally represented as ##STR9##

Fumaric acid-monomethyl ester is structurally represented as ##STR10##

Methyl hydrogen maleate is structurally represented as ##STR11##

Preferred ethylenically-unsaturated carboxylic acid moiety-containingmonomer is selected from the group consisting of acrylic acid,methacrylic acid, and combinations thereof.

Those above-discussed monomers and polymeric ingredients which are usedto make the polymeric ingredient having either acid-functional pendantmoieties, or acetoacetoxy-type functional pendant moieties, or both, aretypically polymerized in the presence of a catalytic amount of aconventional free-radical initiator. Suitable initiators (also called"catalysts") include but are not limited to certain water-solubleinitiators, various azo compounds, and select "redox combinations."

Suitable water-soluble initiators include but are not limited toperacetic acid; certain perborates; certain percarbonates; certainperphosphates; certain persulfates, such as sodium, potassium, ammonium,and barium persulfate; acetyl peroxide; hydrogen peroxide;hydroperoxides such as tertiary-butyl hydroperoxide; and combinationsthereof. A presently preferred water-soluble free-radical initiator isammonium persulfate ("APS").

Suitable azo-type initiators include but are not limited toazodiisobutyl nitrile; azobisdimethyl valeronitrile; azodiisobutylamide; azobis(alpha-ethylbutyl nitrile); azobis(alpha,gamma-dimethyl-capronitrile); and combinations thereof.

One "redox combination," suitable for purposes of the present invention,may consist of a water-soluble persulfate as the "oxidizing" componentof the redox combination, and a hydrosulfite, e.g. sodium hydrosulfite,as the "reducing" component of the redox combination. Further inaccordance with principles of the present invention, water-solublebisulfites, metabisulfites and/or thiosulfates, and formaldehydesulfoxylates, may be used in lieu of the hydrosulfites.

As was briefly mentioned above, one step of a preferred method ofproducing the aqueous polymeric composition-of-matter or formulation ofthe present invention is to combine preselected relative amounts ofinitiator, surfactant, evaporable aqueous carrier andemulsion-polymerizable ingredients in an agitated reactor of suitablesize, and to heat the agitated reactor contents to a desired reactiontemperature over a predetermined period of time, thereby producing anaqueous polymeric emulsion. Optional, chain-transfer agent may also beused at this time, if desired.

During the reaction-hold period--that is, while theemulsion-polymerizable ingredients are addition-polymerizing--it may bedesirable to incorporate certain additional amounts of initiator (orinitiators, if several are used) into the agitated reactor contents, toachieve a desired degree (or percentage) of conversion or reaction ofpolymerizable ingredients. Such additional amounts of initiatoringredient (or initiator ingredients) may be the same as or may bedifferent from the initiator ingredient (or ingredients) selectedinitially. Again, optional chain-transfer agent may be used, if desired.

For purposes of controlling the viscosity value of the polymericformulation, it may be necessary to regulate the molecular weight of thepolymer being formed. This can be accomplished by the incorporation intothe reactor contents of a suitable chain-transfer agent. Suitablechain-transfer agents, to achieve this purpose, are well-known andinclude various halo-organic compounds such as carbon tetrabromide anddibromodichloromethane; sulfur-containing compounds such as theaklylthiols including ethanethiol, butanethiol, tert-butyl and ethylmercaptoacetate, as well as the aromatic thiols; and various otherorganic compounds having hydrogen atoms which are readily "abstracted"by free radicals during polymerization.

The amount of chain-transfer agent needed to achieve a particularmolecular weight, moreover, can be estimated by the use of the "Mayo"equation. (See, e.g., pages 226-233 of a text entitled Principles ofPolymerization, second edition, by George Odian, published 1981 by JohnWiley & Sons, Inc.)

Additional suitable chain-transfer agents or ingredients include but arenot limited to butyl mercapto propionate; iso octyl mercapto propionicacid; iso octyl mercapto propionate ("IOMP"); bromoform;bromotrichloromethane ("BTCM"); carbon tetrachloride; alkyl mercaptanssuch as n-dodecyl mercaptan, tertiary-dodecyl mercaptan, octylmercaptan, tetradecyl mercaptan, and hexadecyl mercaptan; alkylthioglycolates such as butyl thioglycolate, iso octyl thioglycolate, anddodecyl thioglycolate; thioesters; and combinations thereof.

Upon achieving desired reaction conversion, the reactor contents may bemaintained at the initial reaction temperature, or may be cooled to atemperature less than the reaction temperature, as desired.

Upon achieving desired reaction conversion, the pH of the reactorcontents will be less than 7, and typically will be in the range of 2.5to 6. At such pH conditions, the thus-produced addition-polymerparticles, which are typically insoluble in the acidic aqueous phase,may give rise to a latex having a "milky white" appearance. Regardlessof the latex appearance, an effective amount of "base" (as describedbelow) is then added to the reactor contents for preventing gellation.

If the acid value of the thus-produced emulsion polymer is high (i.e.,above about 80 milligrams ("mg") of KOH per gram ("g") of polymersolids), the thus-produced white-appearing latex of the reaction willdissolve and become a clear solution. (The thus-describedemulsion-polymerization reaction typically results in the production ofan alkali-soluble emulsion polymer having both acid-functional andacetoacetoxy-type functional pendant moieties.)

If the acid value of the emulsion polymer is low (below about 80 mgKOH/g of polymer), the polymer will typically not completely dissolvewhen the basic component is added; and the white, milky appearance maythus persist. The polymer particles may become swollen or may berelatively unaffected by the base, depending upon the specific monomersused and the acid value of the polymer.

In any event, the composition-of-matter or formulation thus alsoincludes an amount of base which is effective for providing extendedsingle-package storage stability.

Next incorporated into the aqueous polymeric emulsion presently beingdiscussed is a suitable so-called "non-polymeric" polyfunctionalamine-containing compound having at least two amine-functional moieties.Whereas one skilled in the art would expect the non-polymericpolyfunctional amine ingredient of the formulation to crosslink with theacetoacetoxy-type functional groups via enamine formation, and therebycause gellation, surprisingly, such gellation does not occur. Themechanism for "stabilization" of the formulation is complex and probablyresults from (a) the base competing with the non-polymericpolyfunctional amine in reaction with the acetoacetoxy groups, therebyreducing the degree of crosslinking in the liquid state, and (b) thebase neutralizing carboxylic acid groups on the polymer, thereby formingcarboxylate ions, which would increase the solubility of the polymer andthereby lead to "swelling" rather than to agglomeration.

Laboratory results obtained, to date, however, suggest that at leastsome of the crosslinking--or a major portion of the crosslinking (incertain situations)--may be taking place in the liquid phase, possiblywithin several (i.e., 1 to 4) hours of adding the non-polymericpolyfunctional amine.

Accordingly, while not wanting to be tied to conjecture, yet desirous ofproviding a complete disclosure, it is presently postulated thataddition of base to the reactor contents (1) competes with theamine-functional moieties vis-a-vis the acetoacetoxy-type functionalmoieties, thereby reducing the degree of crosslinking, and/or (2)enhances the colloidal stability of the polymer dispersion which formswhen the crosslinking reaction takes place.

In order to obtain compositions or formulations having superiorstability and which provide coatings possessing superior coatingproperties, it is suggested that the acid value of the polymer bebetween about 30 and 300, and it is preferred that the acid value of thepolymer be between about 50 and 150, which will typically provide analkali-soluble or alkali-swellable polymer. Since the viscosity of theaqueous composition-of-matter or formulation is very molecular-weightdependent, it is preferred that the molecular weight range of theemulsion polymer be relatively low, in order to maintain desired, lowviscosity values at practical "solids" levels.

The weight-average molecular weight ("Mw") of the emulsion polymershould thus be in the range of between about 2,000 and 50,000, andpreferably in the range of between about 2,000 to about 40,000, and morepreferably in the range of between about 2,000 to about 30,000.

For purposes of dissolving such a polymeric ingredient in the aqueouscarrier, it has been found that ammonia, an amine, an alkali metalhydroxide, or various combinations of these may be used, if desired.Suitable amines for such a purpose include but are not limited to methylamine, dimethyl amine, trimethyl amine, ethyl amine, diethyl amine,triethyl amine, propyl amine, dipropyl amine, butyl amine, andcombinations thereof. (It is understood that the term "propyl" mayinclude n-propyl, isopropyl and combinations of these, and that the term"butyl" may include n-butyl, sec-butyl, tert-butyl and combinations ofthese, and so forth.)

In lieu of the above-discussed illustrative preferredemulsion-polymerization method, the emulsion polymerization reaction canalso be conducted, for example, by performing the step of introducing amajor portion of the total amount of initiator, surfactant, optionalchain-transfer agent, and evaporable aqueous carrier into the reactionvessel, in the manner described above, and separately performing thestep of pre-emulsifying the emulsion-polymerizable mixture (brieflydescribed above) in a minor portion of the total amount of initiator,surfactant, optional chain-transfer agent, and evaporable aqueouscarrier, for purposes of producing a so-called "pre-emulsion" mixture;and, thereafter, performing the step of introducing the pre-emulsionmixture into the reaction vessel (already containing the major portionamounts of initiator, surfactant, optional chain-transfer agent, andevaporable aqueous carrier).

In yet another preferred embodiment of the invention, as was brieflymentioned above, the composition-of-matter or formulation of the presentinvention is an aqueous polymeric coating composition which includes amixture of at least two polymeric ingredients. One such polymericingredient includes only acetoacetoxy-type functional pendant moieties;and another polymeric ingredient includes only acid-functional pendantmoieties. Indeed, it is not necessary to have both functionalities in asingle polymeric ingredient, to achieve satisfactory storage stabilityof the formulation as well as satisfactory crosslinkability of theresultant polymeric surface coating. In particular, in the case wherethe formulation contains at least two polymeric ingredients of theabove-described type, each such polymeric ingredient can be preparedaccording to well-known "staged" polymeric reactions. (See, e.g., U.S.Pat. No. 4,325,856 to Ishikawa et al. or U.S. Pat. No. 4,894,397 toMorgan et al.) In that regard, the acetoacetoxy-type functionalmoiety-containing polymeric ingredient may be water-insoluble and/oralkali-insoluble; or the acetoacetoxy-type functional moiety-containingpolymeric ingredient may be rendered water-soluble and/or alkali-solubleby the incorporation of such monomers as acrylamide and/or acrylamidederivatives, hydroxy-functional monomers (such as hydroxyethylacrylate), or other monomers known to impart water-solubility topolymers (such as monomers having ethylene oxide chains of predeterminedlength).

Further in that regard, while the above-described polymeric ingredientsof the present invention are preferably made via conventionalemulsion-polymerization methods, the above-described polymericingredients of the present invention may also be made via conventionalsolution-polymerization or conventional bulk-polymerization methods, ifdesired.

For example, suitable conventional methods for producing thealkali-soluble or alkali-swellable polymeric ingredients of the presentinvention via various well-known solution-polymerization mechanisms aredisclosed e.g. in U.S. Pat. No. 3,673,168 to Burke, Jr., et al.; in U.S.Pat. Nos. 3,753,958 and 3,879,357, both to Wingler et al.; and in U.S.Pat. No. 3,968,059 to Shimada et al. Also, suitable conventional methodsfor producing the polymeric ingredients of the present invention viaconventional bulk-polymerization mechanisms are disclosed in U.S. Pat.No. 4,414,370 to Hamielec et al.; in U.S. Pat. No. 4,529,787 to Schmidtet al.; and in U.S. Pat. No. 4,546,160 to Brand et al.

As was mentioned above, current laboratory observations suggest that theabove-discussed polymeric ingredients containing the acetoacetoxy-typefunctional pendant moieties do crosslink, to some limited degree, withthe amine-functional moieties of the non-polymeric polyfunctional amine,when the latter is added to the formulation; and the failure to observegellation--which would be expected--is currently believed to be a resultof the presence of the "base" ingredient in the reactor contents. Inthat regard, the fact that gellation does not take place is indeedsurprising, particularly in view of the prior art. Nevertheless,regardless of what the prior art would-lead one to expect, theformulations of the present invention exhibit excellent shelf-storagestability, as is clearly evidenced by the absence of gel particles andminimal formulation viscosity change, during extended storage at bothroom temperature and elevated temperatures.

Moreover, as yet another aspect or feature of my present invention, incertain situations it may become desirable to utilize the thus-producedlatex particles (discussed above) as a so-called "support" resin in asubsequent polymerization reaction, before any such non-polymericpolyfunctional amine is incorporated into the reactor contents. It mustbe borne in mind, however, that any such utilization thus reflects apreferred embodiment of my method of making the novel aqueous polymericformulation of my present invention.

In such situations, it will accordingly be desirable to utilize thelatex particles as a so-called "support" resin in a subsequentpolymerization reaction. In that regard, the above-describedpolymerization methods, typically utilized to produce such a latex, arereferred to as "stage one" or the "first stage" of a 2-stagepolymerization procedure; and the thus-produced latex particles arereferred to as the "stage one" polymer.

The subsequent polymerization reaction, thus referred to as "stage two"of the 2-stage procedure, is typically utilized for purposes ofproducing the ultimate film-forming polymeric ingredient or ingredients.Indeed, in the case where the formulation of the invention is anemulsion, and when it is desirable that the discontinuous phase of suchan aqueous polymeric emulsion comprise discreet particles of thefilm-forming polymeric ingredient or ingredients, the latex particlesproduced via the first-stage polymerization reaction are used as a"support" resin in the second-stage polymerization procedure, as isillustrated by the following description.

Accordingly, into the agitated reactor containing the dissolved (orswollen) first-stage latex particles is next added a second monomericmixture specifically so formulated as to produce an addition polymerthat is insoluble in aqueous media having a pH of 2 to 10. Prior toincorporation of the second monomer mixture into the agitated reactor,however, additional water, additional surfactant, additional initiator,and/or additional optional chain-transfer agent, may be added, asdesired. The second monomer mixture is fed into the reaction vessel overa predetermined period of time, typically one hour, while the desiredsecond-stage polymerization reaction temperature is maintained,generally between 40 degrees and 90 degrees Celsius.

The second-stage monomer mixture generally includes at least oneaddition-polymerizable monomer, such as acrylic or methacrylic acidester, a vinyl monomer, a nitrile, or an amide, as describedhereinabove. Furthermore, the second-stage monomer mixture mayoptionally further include an acetoacetoxy-type functionalmoiety-containing monomer, or an acid moiety-containing monomer, orboth, as described hereinabove, if desired.

Still further, to produce the second-stage polymer it may be desirableto incorporate an optional crosslinking ingredient or agent into thereactor contents.

In this regard, crosslinking agents that are suitable for purposes ofthe present invention include but are not limited to divinyl benzene("DVB"), ethylene glycol diacrylate, ethylene glycol dimethacrylate,trimethylol propane triacrylate ("TMPTA"), trimethylol propanetrimethacrylate, pentaerythritol triacrylate, pentaerythritoltrimethacrylate, allyl acrylate, allyl maleate, allyl methacrylate,diallyl maleate, polyethylene glycol diacrylate, and polyethylene glycoldimethacrylate.

Additional crosslinkers, well known to those skilled in the art andsuitable for purposes of my present invention, are disclosed in U.S.Pat. No. 3,915,921 to Schlatzer, Jr.; in U.S. Pat. No. 4,190,562 toWesterman; and in U.S. Pat. No. 4,554,018 to Allen.

During the second-stage reaction-hold period--that is, while theingredients of the second-stage monomer mixture areaddition-polymerizing in the presence of the dissolved or swollen latexparticles of the first-stage polymerization--it may be desirable toincorporate further amounts of initiator into the agitated reactorcontents, to achieve desired conversion of second-stage reaction. Uponachieving desired second-stage reaction conversion, the pH of thereactor contents is suitably adjusted, preferably using aqueous ammoniaor other base, as previously described, to a pH above 7, typically inthe range of 8 to 9.5. At such pH conditions, the aqueous polymericemulsion typically consists of insoluble latex particles of second-stagepolymer, dispersed throughout the continuous phase of the emulsion.

As was briefly noted above, desired crosslinking, in accordance with oneof the several, above-noted features of my present invention, occurswhen the acetoacetoxy-type functional moieties desirably react with theamine-functional moieties of the non-polymeric polyfunctional amine. Aswas "also briefly noted above, the novel water-based polymericcompositions-of-matter or formulations of my invention include aneffective amount of base, for inhibiting undesirable reaction betweenthe acetoacetoxy-type functional pendant moieties of the latex particlesand the amine-functional moieties of the non-polymeric polyfunctionalamine-containing compound, which would otherwise result in gellation.Indeed, desirable reaction, as between these mutually-reactive moieties,does not fully occur until after evaporation of the volatile componentsof the novel aqueous polymeric formulation.

Accordingly, a predetermined amount of the above-mentioned non-polymericpolyfunctional amine having at least two amine-functional moieties may,at this point in time, be introduced into the agitated reactor contents,typically over a time period of 5 to 15 minutes or longer. Thenon-polymeric polyfunctional amine, upon being thus added to the reactorcontents, may dissolve in the continuous phase of the emulsion or maybecome distributed between the continuous and dispersed phases.

In that regard, sufficient non-polymeric polyfunctional amine is thusincorporated into the reactor contents, so as to cause the polymericcomposition therein to typically contain about 0.5 to 1.5acetoacetoxy-type functional pendant moieties per amine-functionalmoiety. Surprisingly, the polymeric composition thus produced is stablefor at least 12 months when stored at room temperature.

The "non-polymeric" polyfunctional amine-containing compound (possessingat least two amine-functional moieties) typically has a chemical-formulaweight of less than about 2,000 grams per mole, and preferably has achemical-formula weight of less than about 1,000 grams per mole.

Referring, briefly, to European Pat. Application Nos. 0 341 886/A2 and 0390 370/A1 (both mentioned above), please note that these Europeanapplications disclose use of polymeric polyfunctional amines ofconsiderably greater chemical-formula weight (or molecular weight) thanthe non-polymeric polyfunctional amine-containing compounds, to which Imake reference herein. It is also important to bear in mind that surfacecoatings of superior physical properties (in accordance with principlesof my present invention), while not able to be made, via inclusion intomy formulation, with polymeric polyfunctional amines, typical of what isdisclosed in the '886 and '370 European applications, were able to bemade when the non-polymeric polyfunctional amine-containing compoundsdiscussed herein were selected. For example, formulations which includedthe non-polymeric polyfunctional amine-containing compounds disclosedherein were observed to be superior in "solvent resistance" to aformulation which included a polymeric polyfunctional amine, asdisclosed in the '886 European patent application.

Accordingly, non-polymeric polyfunctional amines suitable for purposesof the present invention thus include aliphatic and cycloaliphaticamines having 2 to 10 primary and/or secondary amino groups and 2 to 100carbon atoms.

Still further in this regard, suitable non-polymeric polyfunctionalamines include but are not limited to hexamethylene diamine ("HMDA");2-methyl pentamethylene diamine; 1,3-diamino pentane; dodecane diamine;1,2-diamino cyclohexane; 1,4-diamino cyclohexane; para-phenylenediamine; 3-methyl piperidine; isophorone diamine; bis-hexamethylenetriamine; diethylene triamine ("DETA"); and combinations thereof.

Other non-polymeric polyfunctional amines, which are suitable, includethose containing adducts of ethylene and propylene oxide, such as the"JEFFAMINE" series of "D", "ED" and "T" of Texaco Chemical Company ofHouston, Tex., U.S.A. (See, e.g., the inside front covers of the 6 Mayand 24 Jun. 1991, issues of Chemical & Engineering News, published bythe American Chemical Society.)

Preferred non-polymeric polyfunctional amines include 2 to 4 primaryamino groups and 2 to 20 carbon atoms.

Particularly preferred non-polymeric polyfunctional amines includehexamethylene diamine ("HMDA"), diethylene triamine ("DETA"), andcombinations thereof.

Until use is desired, the thus-produced crosslinkable, novel aqueouspolymeric formulation can, for example, be stored at room temperature ina conventional container such as a metal can, a squeezable plastic tube,a glass bottle, an aerosol container, and so forth. When use is desired,the crosslinkable aqueous polymeric formulation is applied to a suitablesubstrate. Evaporation of the evaporable components of the aqueousemulsion then occurs over a predetermined period of time, which istypically governed by ambient conditions. Such evaporation enablesdesirable crosslinking to take place as between the above-discussedmutually-reactive moieties. A crosslinked polymeric surface coating isthus observed to form on the substrate in due course.

DETAILED DESCRIPTION OF EXAMPLES

The following examples are set forth to describe more particularly, tothose skilled in the art, the various principles, features andadvantages of my present invention. As such, they are not intended tolimit my present invention but rather are merely illustrative of certainadvantages of utilizing the novel crosslinkable aqueous compositions orformulations of my present invention, for purposes of producingdesirable crosslinked polymeric surface coatings. Unless otherwiseindicated, references to "percent" shall be understood to mean "weightpercent" based upon total weight.

EXAMPLES 1-5 Coatings Via 1-Stage Polymerization Reactions

The below-listed examples illustrate the utility of the novel aqueousformulation of my present invention, when the formulation does notinclude the second-stage polymeric ingredient briefly mentioned above.(Incidentally, those examples reported herein which include the letter"C" are being reported as "comparative" examples, and thus are beyondthe scope of my present invention.)

The water-based polymeric ingredient-containing formulations of Examples1-5, listed below, were each prepared as follows.

Into a 2-liter, 4-necked flask (or reaction vessel) equipped with athermometer, an agitator, a reflux condenser and a nitrogen ("N₂ ")inlet was charged a solution consisting of 537.4 grams ("g.") ofde-ionized ("DI") water ("H₂ O"), and 8.0 g. of 28 percent ("%") sodiumlauryl sulfate ("NaLS") aqueous anionic surfactant. After heating to 80degrees Celsius ("°C.") under a nitrogen ("N₂ ") atmosphere, 2 g. ofammonium persulfate ("APS") free-radical initiator was added, thetemperature of the reactor contents was maintained at 80° C., and theagitator stirrer was set at 200 revolutions per minute ("RPM"). Next, amixture of the below-listed amounts of monomer and chain-transfer agent(presented in Table I) were pumped into the reactor over a time periodof 30 minutes while maintaining the desired emulsion-reactiontemperature of 80° C.

                  TABLE I                                                         ______________________________________                                        Gram Amounts Of Certain Ingredients In Ex. 1-5                                Ingre-                                                                        dient  Function     Ex. 1  Ex. 2                                                                              Ex. 3C                                                                              Ex. 4C                                                                              Ex. 5                             ______________________________________                                        MMA    Methacrylic  28.4   52.7 51.3  75.6  52.6                                     Acid Ester                                                                    Monomer                                                                BA     Acrylic Acid 50.0   25.7 67.5  43.2  45.9                                     Ester Monomer                                                          MAA    Carboxylic Acid                                                                            16.2   16.2 16.2  16.2  16.2                                     Monomer                                                                AAEM   Acetoacetoxy 40.5   40.5 0.0   0.0   20.3                                     Type Monomer                                                           BTCM   Chain-Transfer                                                                             2.6    2.6  2.6   2.6   2.6                                      Agent                                                                  ______________________________________                                    

The mixture was then held at 80° C. for an additional 30 minutes andthereafter cooled to 25° C., which resulted in the production of alow-viscosity, translucent polymeric emulsion having a pH of 1.7 and asolids content, the latter also being expressed as percent non-volatiles("NV"), of 20.6%. The glass-transition temperature ("Tg") of thethus-produced emulsion polymer is set forth in Table II, below.

                  TABLE II                                                        ______________________________________                                        Glass-Transition Temperature Of Polymer                                       Polymer  Ex. 1    Ex. 2  Ex. 3C  Ex. 4C                                                                              Ex. 5                                  ______________________________________                                        Tg, °C.                                                                         10       40     10      40    25                                     ______________________________________                                    

To the polymeric emulsions of Examples 1-5 were added the gram-amountsof ingredients set forth in Table III below, thereby resulting in theproduction of five (5) aqueous polymeric solutions.

                  TABLE III                                                       ______________________________________                                        Gram Amounts Of Base And Polyfunctional Amine                                 Ingredient                                                                            Function Ex. 1   Ex. 2                                                                              Ex. 3C Ex. 4C                                                                              Ex. 5                              ______________________________________                                        NH.sub.3.sup.a/                                                                       Base     12.8    12.8 12.8   12.8  12.8                               HMDA.sup.b/                                                                           PFA.sup.c/                                                                             11.0    11.0 0.0    0.0   5.5                                ______________________________________                                         Footnotes:                                                                    .sup.a. The ammonia ("NH.sub.3 ") utilized was 2.5% aqueous NH.sub.3.         .sup.b. The hexamethylene diamine ("HMDA") utilized was 10% aqueous HMDA.     .sup.c. The function of the HMDA was as a "nonpolymeric" polyfunctional       amine ("PFA").                                                           

In each aqueous polymeric solution of Examples 1, 2 and 5 thethus-produced formulation contained an average ratio of one (1)acetoacetate-type functional moiety to one (1) amine-functional moiety.

Examples 3C and 4C, on the other hand, contained neitheracetoacetoxy-type functional moiety nor amine-functional moiety. Indeed,examples 3C and 4C are presented for "comparison" purposes only,vis-a-vis Examples 1, 2 and 5 (which are illustrative of certainfeatures and advantages of my present invention).

A portion of the thus-produced aqueous polymeric solutions of Examples1-5 were set aside at room temperature for 12 hours, and were thereaftercast on "Leneta" charts, using a #4 wire-wound rod, for purposes ofproviding polymeric films of approximately 0.3 mils thickness.

Procedure

A "Leneta" test chart was attached to a commercially available"impression" bed, for each polymeric solution that was to be tested.Aqueous polymeric solution was then spread along the top and across thewidth of each bed-attached chart. Taking the wire-wound rod in bothhands, the "drawdown" of each such polymeric solution was nextdetermined, beginning at the top of each chart, above the location ofthe thus-applied liquid product. The rod was then drawn downwardly,without rolling, at a steady rate, thereby causing the liquid product tobecome spread across the chart.

The thus-produced polymeric films were all dried, both at roomtemperature ("R.T.") overnight (about 8 to 10 hours) and in an oven setat 60° C. for 5 minutes.

The physical properties of the thus-produced polymeric surface coatingswere evaluated, with results appearing in Table IV, below.

                  TABLE IV                                                        ______________________________________                                        Film Properties Of Examples 1-5                                               Film Drying                                                                            Film Test                                                            Procedure                                                                              Procedures Ex. 1  Ex. 2                                                                              Ex. 3C                                                                              Ex. 4C                                                                              Ex. 5                             ______________________________________                                        Air Dried                                                                              Acetone-   5      5    1     1     3                                 At R.T.  Resistance                                                           Overnight                                                                              Alcohol-   5      5    1     1     3                                          Resistance                                                                    0.1% Aq.   5      5    1     1     3                                          NH.sub.3                                                                      Resistance                                                           Oven Dried                                                                             Acetone-   5      5    1     1     5                                 at 60° C.                                                                       Resistance                                                           for 5 Min.                                                                             Alcohol-   5      5    1     1     5                                          Resistance                                                                    0.1% Aq.   5      5    1     1     5                                          NH.sub.3                                                                      Resistance                                                           ______________________________________                                         The film "test procedures" listed in Table IV (above) are described below     In Table IV, the term "alcohol" means 60 weight percent aqueous ethyl         alcohol.                                                                 

The film "test procedures" listed in Table IV (above) are describedbelow. In Table IV, the term "alcohol" means 60 weight percent aqueousethyl alcohol.

Acetone Resistance

Directly onto each above-noted coating was applied a drop of acetone,from an eye dropper. After such contact for 10 seconds, the acetone wascarefully removed from each coating with a cloth, and visually rated, asdescribed below.

Alcohol Resistance

Directly onto each coating was applied a drop of 60% aqueous ethylalcohol, from an eye dropper; and such was then covered with acommercially available eye glass. After such contact for 60 minutes, thealcohol was carefully removed from each coating with a paper towel andvisually rated, after a subsequent "recovery" time period of 60 minutes.

Aqueous Ammonia Resistance

Directly onto each coating was applied a drop of 0.1 wt.-% aqueousammonia, from a commercially available eye dropper. After such contactfor 1 minute, the aqueous ammonia was carefully removed from eachcoating with a paper towel and visually rated, after a subsequent"recovery" time period of 60 minutes.

Visual Rating

Each thus-tested polymeric coating was visually rated, for "degree" ofspot development and to observe whether any "degradation" or"solubilization" of the coating had resulted, after thus being contactedwith acetone, alcohol and aqueous ammonia, in the manner describedabove.

The polymeric films were thus visually rated on a "spot"-test scale of"1" to "5", with "5" indicating no effect of the solvent on the coating.A "3" indicated that a "strong" spot was visible, but that thestructural integrity of the film did not appear to have changed. A "1"indicated complete solubilization of the coating by the indicatedsolvent.

Storage Stability

Another portion of the above-described polymeric emulsions of Examples1-5 were separately stored for six (6) weeks at 50° C.; and thereafterat room temperature ("R.T.") for about one (1) year. Films weresubsequently cast onto so-called "Leneta" charts utilizing proceduresdescribed above, and solvent-resistance tests were performed (alsoutilizing procedures described above), with the results being summarizedin Table V, below.

                  TABLE V                                                         ______________________________________                                        Film Properties After Storage Of Liquid                                       Formulations For About 12 Months                                              Film Drying                                                                            Film Physical                                                        Procedure                                                                              Property   Ex. 1  Ex. 2                                                                              Ex. 3C                                                                              Ex. 4C                                                                              Ex. 5                             ______________________________________                                        Air Dried                                                                              Acetone-   5      5    1     1     3                                 At R.T.  Resistance                                                           Overnight                                                                              Alcohol-   5      3    1     1     3                                          Resistance                                                                    0.1% Aq.   5      3    1     1     3                                          NH.sub.3                                                                      Resistance                                                           Oven Dried                                                                             Acetone-   5      5    1     1     3                                 At 60° C.                                                                       Resistance                                                           For 5 Min.                                                                             Alcohol-   5      3    1     1     3                                          Resistance                                                                    0.1% Aq.   5      3    1     1     3                                          NH.sub.3                                                                      Resistance                                                           ______________________________________                                    

EXAMPLES 6-9 Coatings Via 2-Stage Polymerization

A presently preferred two-stage polymerization procedure is described asfollows.

Into a 2-liter, 4-necked flask (or reaction vessel) equipped with athermometer, an agitator, a reflux-condenser and a nitogen inlet wascharged 490.0 grams ("g.") of de-ionized ("DI") water ("H₂ O") and 8.0g. of 28% sodium lauryl sulfate ("NaLS") aqueous anionic surfactantsolution. The flask headspace was blanketed with the inert gas, nitrogen("N₂ "), as the flask contents were heated to 80 degrees Celsius("°C.").

A so-called "premix" was prepared separately, simply by combining thevarious (below-indicated) ingredients at room temperature. The premixincluded the monomer mixture and chain-transfer agent identified inTable VI, below.

                  TABLE VI                                                        ______________________________________                                        Premix Ingredients                                                            Ingredients                                                                              Function           Grams                                           ______________________________________                                        MMA        Methacrylic Ester Monomer                                                                        52.94                                           AAEM       Acetoacetoxy Type Monomer                                                                        33.09                                           BA         Acrylic Ester Monomer                                                                            30.44                                           MAA        Acid-Functional Monomer                                                                          15.88                                           BTCM       Chain-Transfer Agent                                                                             2.60                                            ______________________________________                                    

With the agitator stirrer set at 200 revolutions per minute ("RPM"), 15%(20 g.) of the premix of Table VI was added to the reactor contents,followed by 2.0 g. of ammonium persulfate ("APS") free-radical initiatordissolved in 10.0 g. of de-ionized water. After holding the reactorcontents at the desired reaction temperature of 80° C. for 10 minutes,the remainder of the "premix" of Table VI was pumped into the reactorover a 30-minute time period. Thereafter, the resulting polymericemulsion was held at 80° C. for an additional 10-minute time periodbefore continuing with the second-stage portion of the 2-stagepolymerization reaction. The pH of the polymeric emulsion in the reactorwas determined to be 2.5. The first-stage polymeric emulsion had asolids content of 21.5% NV; and the first-stage emulsion polymer wasfound to have a Tg of 38° C.

Immediately following the 10-minute "hold" period and while the reactorcontents were being maintained at 80° C., a portion of the polymericemulsion from the above-discussed first-stage polymerization reactionwas partially-neutralized, from 2.5 pH to 5.2 pH, by adding 2.5 g. of25% aqueous ammonia ("aq. NH₃ ") dissolved in 10.0 g. of de-ionizedwater. Five minutes thereafter, a second-stage monomer mixtureconsisting of 226.8 g. styrene ("St") monomer, 44.1 g. 2-ethylhexylacrylate ("2-EHA") monomer, and 44.1 g. butyl acrylate ("BA") monomerwas incorporated into the reactor contents over a 60-minute time periodwhile maintaining the reactor contents at the desired 80° C. reactiontemperature. Immediately following the addition of the second-stagemonomer mixture, the reactor contents were maintained at 80° C. for anadditional 10-minute hold period. The pH of the reactor contents was5.0. Thereafter, 10.1 g. of 25% aqueous ammonia ("aq. NH₃ ") dissolvedin 10.3 g. of de-ionized water was incorporated into the reactorcontents over a time period of 4 minutes, while maintaining the reactorcontents at the desired reaction temperature of 80° C., thereby changingthe pH of the reactor contents from 5.0 to 7.6. Immediately followingthe ammonia addition, the reactor contents were maintained at 80° C. foran additional 50-minute hold period. The reactor contents were nextcooled to room temperature. The polymeric emulsion thus produced was awhite, fluid latex having a pH of 7.6 and a minimum film-formingtemperature ("MFT") of 45° C.

Then, four coating compositions (Examples 6-9) were prepared from theabove-described latex as follows. In particular, the coatingcompositions were prepared by first adding a specified coalescingsolvent, namely the monobutyl ether of ethylene glycol, to theabove-described latex at room temperature at the rate of 8.0 g. ofcoalescing solvent over a 1-minute time period, and in the ratio amountof 8.0 g. of coalescing solvent per 100 g. of latex. Then, the various,below-indicated amounts of 10% aqueous hexamethylene diamine ("HMDA")non-polymeric polyfunctional amine and de-ionized ("DI") water wereincorporated into 54.0 g. portions of the above-described latex, aspresented in Table VII, below.

                  TABLE VII                                                       ______________________________________                                        Coating Formulation Ingredients                                               Example  10% AQ. HMDA   DI Water  Ratio.sup.d/                                ______________________________________                                        No. 6    0              0         0.0                                         No. 7    0.224 g.       5 g.      0.5                                         No. 8    0.448 g.       5 g.      1.0                                         No. 9    0.672 g.       5 g.      1.5                                         ______________________________________                                         .sup.d. "Ratio" means the ratio of aminefunctional moieties to                acetoacetoxytype functional moieties, present in the coating formulation      of each of Examples 6-9.                                                 

A portion of the above-described coating formulations (Examples 6-9)were applied to 4-inch by 6-inch (about 10-centimeter by 15-centimeter)glass plates, using a #22 wire-wound rod, to produce several sets ofsurface coatings. One such set of surface coatings was allowed toair-dry at room temperature for 4 days prior to having its physicalproperties evaluated. Another such set of surface coatings was dried at60° C. in an oven for 5 minutes and thereafter allowed to stand at roomtemperature for 4 days prior to having its physical propertiesevaluated. The polymeric films thus produced (which were clear,incidentally) were tested for solubility in acetone solvent andtetrahydrofuran ("THF") solvent by scraping portions of the polymericfilm from the glass plates and immersing the thus-scraped film portionsin each of the above-mentioned solvents for a time period of 24 hours.The glass plate-applied polymeric films were separately "spot"-testedwith alcohol (in accordance with procedures set forth in Exs. 1-5above). The glass plate-applied polymeric films were also tested forKonig hardness on a commercially-available "hardness" tester.

DIN 53157 was the procedure that was used to measure hardness. Konighardness values are reported in "seconds".

                  TABLE VIII                                                      ______________________________________                                        Physical Properties Of Polymeric Films Produced                               From 2-Stage Polymerization Methods                                           Film                                                                          Drying                                                                        Pro-  Film Physical                                                           cedure                                                                              Properties Ex. 6    Ex. 7  Ex. 8  Ex. 9                                 ______________________________________                                        No. 1.sup.e/                                                                        Acetone    dissolved                                                                              swelled                                                                              swelled                                                                              swelled                                     Solubility                                                                    THF Solu-  dissolved                                                                              swelled                                                                              swelled                                                                              swelled                                     bility                                                                        Alcohol    2        2      2      2                                           Resistance                                                                    Konig      180      216    213    204                                         Hardness                                                                No. 2.sup.f/                                                                        Acetone    dissolved                                                                              swelled                                                                              swelled                                                                              swelled                                     Solubility                                                                    THF Solu-  dissolved                                                                              swelled                                                                              swelled                                                                              swelled                                     bility                                                                        Alcohol    2        5      5      5                                           Resistance                                                                    Konig      194      216    215    210                                         Hardness                                                                ______________________________________                                         Footnotes:                                                                    .sup.e. Procedure "No. 1" means the film was airdried at room temperature     over a 4day time period.                                                      .sup.f. Procedure "No. 2" means the film was ovendried at 60 degrees          Celsius over a 5minute time period, and thereafter at room temperature fo     a 4day time period.                                                      

The alcohol-resistance test was conducted, as described above inconnection with Examples 1 through 5, except that the contact time was15 minutes.

The "hardness" value was determined via the above-mentioned "DIN 53157"test procedure, which is also referred to as the "Konig" pendulum test.(The "Konig" value, the amount of time that a particular pendulum isswinging, is typically reported in seconds.)

Another portion of the above-described polymeric coating formulations(Examples 6-9) was stored at room temperature for four (4) months.Thereafter, "new" polymeric films were applied to glass plates, driedand evaluated, as described above. The resulting polymeric film-propertydata of the coating formulations that had been stored at roomtemperature for four (4) months were virtually identical to the data setforth in Table VIII, above, and thus need not be re-tabulated.

EXAMPLE 10 2-Stage Polymerization With Crosslinker Agent

This particular example illustrates optional use of a conventionalcrosslinker agent, via incorporation into the novel aqueouscomposition-of-matter of my invention.

The first-stage polymerization described above in connection withExamples 6-9 was repeated, except that a monomer mixture consisting of28.4 g. methyl methacrylate ("MMA") monomer, 44.5 g. butyl acrylate("BA") monomer and 16.2 g. acetoacetoxyethyl methacrylate ("AAEM")monomer was utilized in the first-stage polymerization. Thereafter, thesecond-stage polymerization procedure described above was substantiallyfollowed, except that the second-stage monomer mixture consisted of 189g. styrene ("St") monomer, 59.9 g. 2-ethylhexyl acrylate ("2-EHA")monomer, 59.9 g. butyl acrylate ("BA") monomer, 31.5 g.acetoacetoxyethyl methacrylate ("AAEM") monomer, and 31.5 g. oftrimethylolpropane triacrylate ("TMPTA") crosslinker agent.

The end-result of thus-employing a two-stage polymerization procedurewas a white, fluid latex having a solids content of 44.4 % NV; a pH of7.4; a Brookfield viscosity of 210 centipoises ("cPs."), utilizing a #2spindle at 30 RPM, 20° C.; and a minimum film-forming temperature("MFT") of 18° C. The procedure utilized to determine minimumfilm-forming temperature was ASTM D 2354-86.

To a 50-gram portion of the thus-produced latex were added 5.9 g. of 10%aqueous HMDA and 5 g. of de-ionized water, to produce sample "A"; and toanother 50-gram portion of the latex was added 5 g. of de-ionized wateronly, to produce sample "B".

Samples "A" and "B" were then utilized as polymeric coatingformulations. In particular, samples "A" and "B" were applied to glassplates and "Leneta" charts, in accordance with procedures set forthabove, utilizing a #22 wire-wound rod, to produce polymeric films on theglass plates; and the glass plate-applied polymeric films were thenoven-dried at 60° C. for 5 minutes. Thereafter, the Konig hardness valueof each such (now-dry) polymeric film was determined immediatelyfollowing removal from the oven and cool-down to room temperature, andfour (4) days thereafter, with the observed results being reported asfollows.

                  TABLE IX                                                        ______________________________________                                        Comparison Of Example 10 Samples                                              Konig Hardness  Sample A  Sample B                                            ______________________________________                                        Initial         198       176                                                 4 Days          212       185                                                 ______________________________________                                    

The "Leneta" chart coatings were tested for blocking resistance. Theterm "blocking resistance" means the ability to resist fusion togetherunder specified temperature and pressure conditions.

The procedure to determine blocking resistance is described as follows.The "Leneta" chart-applied polymeric films were placed face-to-face andwere thereafter subjected to a pressure of 100 g. per square centimeterfor 3 days at 40° C., and thereafter visually inspected. (In thiscontext, the term "face-to-face" means coated side on coated side.) Theresults are tabulated as follows.

                  TABLE X                                                         ______________________________________                                        Blocking Of Example 10 (Sample) Films                                         Leneta Charts Sample A   Sample B                                             ______________________________________                                        Ex. 10 Films  No Blocking                                                                              Total Blocking                                       ______________________________________                                    

In Table X (above) the term "no blocking" in the context of the"blocking-resistance" test, means that the coatings did not fusetogether. In particular, the coatings could readily be removed from eachother without damaging the surface of the coatings.

The term "total blocking", also in the context of the"blocking-resistance" test, means that the coatings fused togethercompletely and could not be removed from each other without damaging thesurface of the coatings.

EXAMPLE 11 Parquet Floor Lacquer Via 2-Stage Method

The first-stage polymerization procedure of Examples 6-9 wassubstantially repeated, except that the amounts of monomer andchain-transfer agent reported in Table XI (below) were utilized toproduce the first-stage polymer of this particular example, whichillustrates utility of the aqueous formulation of my invention as alacquer for parquet floors. The optional chain-transfer agent used wasiso octyl mercapto propionate ("IOMP").

                  TABLE XI                                                        ______________________________________                                        First-Stage Polymerization Ingredients                                        Ingredient                                                                            Function             Amount, Grams                                    ______________________________________                                        BA      Acrylic Acid Ester Monomer                                                                         58.1                                             AAEM    Acetoacetoxy-type Monomer                                                                          40.5                                             MMA     Methacrylic Acid Ester Monomer                                                                     20.3                                             MAA     Carboxylic Acid Monomer                                                                            16.2                                             IOMP    Chain-Transfer Agent 4.1                                              ______________________________________                                    

The first-stage polymeric emulsion had a solids content of 21.0% NV anda pH of 2.5. The first-stage emulsion polymer had a Tg of 0° C.

Thereafter, the second-stage polymerization procedure of Examples 6-9was substantially repeated, except that the monomer mixture of Table XII(below) was used as the second-stage monomer feed. In the second-stagepolymerization, the optional crosslinking agent used was divinyl benzene("DVB").

                  TABLE XII                                                       ______________________________________                                        Second-Stage Polymerization Ingredients                                       Ingredient                                                                             Function           Amount, Grams                                     ______________________________________                                        St       Vinylic Monomer    189.0                                             BA       Acrylic Acid Ester Monomer                                                                       63.0                                              2-EHA    Acrylic Acid Ester Monomer                                                                       63.0                                              DVB      Crosslinking Agent 1.6                                               ______________________________________                                    

The end-result of my thus-employing a two-stage polymerization procedurewas a white, fluid latex having a solids content of about 45% NV, a pHof 7.6, a Brookfield viscosity (utilizing a #2 spindle at 30 RPM, 20°C.) of 110 mpas, and a minimum film-forming temperature ("MFT") of 21°C. (The term "mpas", which means milliPascal-seconds, is the so-calledPSI System" terminology for viscosity. In this regard, 1 mpas is definedas 1 cP (centiPoise).) The thus-produced emulsion polymer was found tohave a glass-transition temperature of 13° C.

To a 60-gram portion of the thus-produced latex was added and blended12.5 g. of a 5% aqueous solution of hexamethylene diamine ("HMDA"), 8.5g. of a commercially-available aqueous dispersion of polyethylene wax,16 g. of water, and a 3.0-g. quantity of that coalescing solventmentioned above in connection with Examples 6-9, namely the monobutylether of ethylene glycol.

A portion of the thus-resulting aqueous formulation was then applied toa parquet floor, and thereafter allowed to dry to a crosslinkedpolymeric film. The resulting crosslinked polymeric film was observed toprovide the parquet floor with a relatively high-gloss finish which wasfurther observed to maintain its high-gloss and otherwise desirableappearance during four (4) months of moderate-to-heavy pedestriantraffic.

Another portion of the above-described aqueous formulation (of Example11) was stored for six (6) months at room temperature and, thereafter,the aqueous formulation was applied to glass slides and "Leneta" charts,utilizing procedures substantially set forth hereinabove, except that a#26 wire-wound rod was used. After allowing the thus-applied polymericfilms to dry overnight (about 8 to 10 hours) at 20° C., the 60-degreespecular gloss value of the "Leneta" chart coating was determined to be89, and certain solvent-resistance tests were performed upon thepolymeric films, with the results being reported in Table XIII, below.The test term "specular" relates, in general, to the mirror-like orreflective property of the substrate-applied polymeric film. The"specular gloss" of the thus-produced polymeric films was measured usinga commercially-available so-called "BYK-Mallinkrodt" 60-Degree pocketglossmeter. Glossmeter readings were taken across the entire treatedfloor surface, and the readings were thereafter averaged.

                  TABLE XIII                                                      ______________________________________                                        Evaluation Of Film Properties                                                 Film Property    Observation                                                  ______________________________________                                        Acetone Resistance                                                                             5                                                            10% Aq. NH.sub.3 Resist.                                                                       5                                                            H.sub.2 O Resist., 60 Min.                                                                     5                                                            ______________________________________                                    

The numerical value assigned to each above-listed "observation" as wellas the procedures for determining acetone resistance, the resistance of10% aqueous ammonia ("NH₃ "), and water resistance, are allsubstantially as set forth above, except that the contact time fordetermining resistance of aqueous ammonia and water are 5 minutes and 60minutes, respectively.

EXAMPLE 12C Formulation Lacking Acid-Functional Monomer

Coating formulations made without an acid-functional monomer are outsidethe scope of this invention and have poor storage stability, as is shownby the following.

As an illustration, yet another coating formulation was prepared,substantially repeating the procedures set forth above for Example 1,except that the ingredients utilized were as set forth in Table XIV,below.

                  TABLE XIV                                                       ______________________________________                                        Example 12C Formulation                                                                                      Amount,                                        Ingredient                                                                              Function             Grams                                          ______________________________________                                        DI Water  Carrier              712.3                                          BA        Acrylic Acid Ester Monomer                                                                         110.7                                          AAEM      Acetoacetoxy-type Monomer                                                                          90.2                                           MMA       Methacrylic Acid Ester Monomer                                                                     63.2                                           28% Aq. NaLS                                                                            Anionic Surfactant   16.0                                           BTCM      Chain-Transfer Agent 5.7                                            ______________________________________                                    

The resulting polymeric emulsion was a white, fluid latex possessing asolids content of about 27% NV, a pH of 2.0, a Brookfield viscosity(utilizing a #2 spindle at 30 RPM, 20° C.) of 5 mpas, and a minimumfilm-forming temperature ("MFT") of less than 0° C. The thus-producedemulsion polymer was found to have a glass-transition temperature ofminus 8° C.

To a 100-g. sample of this Example 12C latex was added 2.49 g. of 25%aqueous ammonia ("NH₃ "), 20.0 g. of de-ionized water, and 21.3 g. of a10% aqueous solution of hexamethylene diamine ("HMDA"), which changedthe pH to 11.6.

The thus-produced latex was observed to gel in about 12 hours, at roomtemperature; and the resulting gel was observed to be insoluble inacetone.

EXAMPLE 13 Separate Polymer Possessing COOH-Functionality

On the other hand, utilization of a polymeric emulsion possessingCOOH-functionality in a separate polymer is within the scope of mypresent invention; and the following example is illustrative.

To a second 100-g. sample of the latex of Example 12C was added 3.64 g.of 25% aqueous ammonia ("NH₃ "), 87.8 g. of a 30% aqueous solution of analkali-soluble polymer having an acid value of 78, 64 grams ofde-ionized water, and 21.3 g. of 10% aqueous hexamethylene diamine("HMDA"). The above-mentioned polymer, made in accordance with U.S. Pat.No. 4,529,787, consisted of 25 mole % styrene monomer, 50 mole % methylmethacrylate monomer, 15 mole % butyl acrylate monomer, and 10 mole %acrylic acid monomer. The above-named ingredients were mixed into thesecond 100-g. sample of the Example 12C latex formulation, at roomtemperature, and in the order mentioned.

The resulting polymeric emulsion was found to have an initial viscosityof 5 cPs. and a pH of 9.8. After four (4) weeks storage at 50° C., theviscosity of the thus-produced polymeric emulsion was observed to remainsubstantially at 5 cPs. and the pH was observed to remain at 9.8.

The thus-described polymeric emulsion (of Example 13) was then utilizedto produce polymeric films on Leneta charts, utilizing proceduresdescribed above; and such polymeric films, made from "fresh" polymericemulsion as well as those made from the 4-weeks aged polymeric emulsion,were found to possess desirable acetone-resistance properties.

EXAMPLE 14 Pigmented Coatings Via 2-Stage Polymerization

This example illustrates the use of a known core-shell polymerizationmethod (as is presently described in U.S. Pat. No. 4,894,397 to Morganet al.) to prepare crosslinkable, pigmented coatings, in accordance withprinciples of the present invention. The procedure utilized is describedas follows.

To a 1-liter, 4-necked flask fitted with a thermometer, an agitator, areflux-condenser and a nitrogen inlet was added 480 g. of de-ionized("DI") water ("H₂ O") and 0.5 g. of the anionic surfactant sodium laurylsulfate ("NaLS"), under an inert-gas atmosphere of nitrogen ("N₂). Afterheating the reactor contents to 80° C., while setting the agitatorstirrer at 200 revolutions per minute ("RPM"), 1.0 g. of thefree-radical initiator ammonium persulfate ("APS") was incorporated intothe reactor contents.

Thereafter, over a 30-minute period of time was added a first-stagemonomer mixture consisting of 50 g. of ethyl acrylate ("EA") monomer, 30g. of acetoacetoxyethyl methacrylate ("AAEM") monomer, 20 g. ofmethacrylic acid ("MAA") monomer, and 2 g. of the optionalchain-transfer agent butyl mercapto propionate. A 15-minute "hold"period followed the monomer mixture addition.

The first-stage polymeric emulsion had a solids content of 16.8% NV anda pH of 2.4. The first-stage emulsion polymer had a Tg of 18° C. Afterthe 15-minute "hold" period, 100 g. of methyl methacrylate ("MMA")monomer, the second-stage monomer, was added over an additional30-minute period of time. The resultant latex was held at 80° C. for 60additional minutes, before cooling to room temperature. The resultantlatex was found to have a solids content of 27.7% NV and a pH of 2.7.Thereafter, two (2) separate 200-g. portions of the thus-produced latexwere neutralized, each with 8.5 g. of 28% aqueous ammonia, to a pH of8.7.

One of the thus-neutralized latexes was utilized as a first paint("Paint A"). The second of the thus-neutralized latexes had 22.2 g. of10% aqueous hexamethylene diamine ("HMDA") incorporated thereinto andthereafter was used to make a second paint ("Paint B").

Paints "A" and "B" were formulated, each with 33.0 g. of titaniumdioxide ("TiO₂ ") and 40.1 grams of thus-produced emulsion solids, toproduce 200 grams of conventional, white paints, each of about 37.4% NV.Such paints were applied to commercially-available, anodized aluminumpanels, utilizing a #36 wire-wound rod.

Paints "A" and "B" each dried to a polymeric film having a filmthickness of about 1.0 mil. (A "mil" is understood to meanone-thousandth, 0.001, of an inch. An inch is equivalent to 2.54centimeters.) After the panel-applied films had been allowed to dryovernight (about 16 hours), the resulting, crosslinked polymeric filmswere subjected to a particular solvent-resistance test (MEK rubs). Thethus-tested-panel-applied films were subsequently aged for seven (7)additional days at room temperature and were then again subjected to theabove-noted solvent-resistance test.

"MEK Rubs" Procedure

A piece of cloth, wetted with MEK (methyl ethyl ketone), is rubbed backand forth, with the forefinger under moderate pressure, over the coatedsubstrate, until a part of the coating comes loose from the substrate.The piece of cloth is re-wetted from time to time, to maintain a wetsurface.

The results of the solvent-resistance test described above are set forthin Table XV, below.

                  TABLE XV                                                        ______________________________________                                        Solvent-Resistance Data                                                       MEK Rubs      Paint "A" Paint "B"                                             ______________________________________                                        16 Hrs.       3         23                                                     7 Days       23        211                                                   ______________________________________                                    

The above data concerning Paint "B" illustrates the superiorsolvent-resistance effects of crosslinking.

EXAMPLE 15C Latex Containing Acetoacetoxy Monomer

As the prior art suggests, there are many known latexes which might orwhich can contain an acetoacetoxy-type functional monomer. There is,however, no prior-art reference (to my knowledge) that discloses or evensuggests my invention. In that regard, the following "comparative"example, Example 15C, describes the preparation of a certain latex whichcontains acetoacetoxy-type functional monomer, but not acid functionalmonomer. This comparative example is beyond the scope of my presentinvention.

Into a 1000-milliliter ("ml.") 4-necked flask fitted with areflux-condenser, a thermometer and a variable-speed agitator wascharged 487 g. of de-ionized water ("H₂ O") which was heated to 80° C.,while the flask was being sparged with the inert gas nitrogen ("N₂ ").As soon as the reactor contents achieved a temperature of 80° C., 9.05g. of "DOWFAX 2A1" (brand) surfactant and 0.87 g. of the free-radicalinitiator ammonium persulfate ("APS") were added. "DOWFAX 2A1" (brand)liquid surfactant, technically referred to as a sodium dodecyldiphenyloxide disulfonate, has a hydrophile-lipophile balance ("HLB")value of 16.7, and is commercially available from Dow Chemical Companyof Midland, Mich., at a concentration of 45%.

Following addition of the above-identified free-radical initiator, andwhile maintaining the reactor contents at 80° C., a monomer mixtureconsisting of 109.14 g. of methyl methacrylate ("MMA") monomer, 94.59 g.of butyl acrylate ("BA") monomer, and 87.32 g. of acetoacetoxyethylmethacrylate was pumped into the reactor over a time period of 75minutes. Immediately following addition of the monomer mixture, theagitated reactor contents were held at 80° C. for an additional 60minutes and were thereafter cooled to room temperature. Thethus-produced latex was found to be 35.78% NV, and was found to have apH of 2.5, and a Brookfield viscosity (#2 spindle, at 25° C. and 60 RPM)of 19 cPs. The latex was neutralized to 8.5 pH with 30% ammoniumhydroxide, and a stoichiometric amount of hexamethylene diamine ("HMDA")was added while stirring. In particular, 2.22 g. of 10% HMDA in waterwas mixed with 27.82 g. of latex. The resulting (mixed) formulationgelled in about one (1) hour.

A novel aqueous polymeric composition-of-matter has been describedhereinabove. Also described hereinabove are methods of making the novelpolymeric composition-of-matter, as well as methods of utilizing thenovel polymeric composition-of-matter, for purposes of producing desiredcrosslinked surface coatings and films on various substrates. Whilethese various aspects of my present invention have been describedhereinabove with respect to certain preferred embodiments andillustrative examples, it is to be understood that the scope of mypresent invention is not to be limited to such embodiments and examples.On the contrary, a variety of alternatives will become apparent to thoseskilled in the art upon reading the foregoing description. For exampleand in connection with the two-stage polymerization procedures discussedabove, either the first-stage polymerization or the second-stagepolymerization, or both polymerization steps, may incorporate either theacid-functional monomer or the acetoacetoxy-type functional monomer(described above), in accordance with the principles of the presentinvention. Accordingly, such alternatives, changes and/or modificationsare to be considered as forming a part of my present invention insofaras they fall within the spirit and scope of the appended claims.

I claim:
 1. A method of producing a novel aqueous polymeric formulation,comprising the steps of:admixing at least one polymeric ingredient, anon-polymeric polyfunctional amine, and base, in an evaporable aqueouscarrier, wherein the polymeric ingredient has both acid-functionalpendant moieties and pendant moieties having the ability to form stableenamine structures by reaction with amines and contain a divalent groupof the structure ##STR12## wherein R₁ is either H, a C₁ to C₁₀ alkylgroup, or phenyl, wherein the non-polymeric polyfunctional amine has atleast two amine-functional moieties, and wherein the amount of base inthe aqueous carrier is effective for inhibiting gellation, which wouldotherwise occur as a result of crosslinking between the pendant moietieshaving the ability to form stable enamine structures andamine-functional moieties, thereby producing a reaction mixture; holdingthe reaction mixture at a preselected reaction temperature for apredetermined period of time, thereby producing the aqueous evaporablepolymeric formulation.
 2. A method of producing a novel aqueouspolymeric formulation, comprising the steps of:admixing at least twopolymeric ingredients, a non-polymeric polyfunctional amine, and base,in an evaporable aqueous carrier, wherein one of the two polymericingredients has acid-functional pendant moieties and the other of thetwo polymeric ingredients has pendant moieties having the ability toform stable enamine structures by reaction with amines and contain adivalent group of the structure ##STR13## wherein R₁ is either H, a C₁to C₁₀ alkyl group, or phenyl, wherein the non-polymeric polyfunctionalamine has at least two amine-functional moieties, and wherein the amountof base in the formulation is effective for inhibiting gellation, whichwould otherwise occur as a result of crosslinking between the pendantmoieties having the ability to form stable enamine structures andamine-functional moieties, thereby producing a reaction mixture; holdingthe reaction mixture at a preselected reaction temperature for apredetermined period of time, thereby producing the aqueous evaporablepolymeric formulation.
 3. The method of either claim 1 or claim 2wherein the pendant moieties having the ability to form stable enaminestructures present in the polymeric ingredient are derived from amonomeric ingredient represented by the following structure: ##STR14##wherein R₁ is either H, a C₁ to C₁₀ alkyl group, or phenyl; wherein A iseither: ##STR15## wherein R₂ is either H, a C₁ to C₁₀ alkyl group,phenyl, halo, CO₂ CH₃, or CN;wherein R₃ is either H, a C₁ to C₁₀ alkylgroup, phenyl, or halo; wherein R₄ is either a C₁ to C₁₀ alkylene group,or phenylene; wherein R₅ is alkylene; wherein any of "a", "m", "n", and"q" is either 0 to 1; wherein each of "X" and "Y" is either --NH-- or--O--; and wherein "B" is either "A", a C₁ to C₁₀ alkyl group, phenyl,or heterocyclic.
 4. A method of producing a novel aqueous polymericformulation, comprising the steps of:producing a single package aqueousevaporable polymeric formulation that is stable for extended periods oftime by admixing ingredients consisting essentially of at least onepolymeric ingredient, a non-polymeric polyfunctional amine, and base, inan evaporable aqueous carrier, wherein the polymeric ingredient has bothacid-functional pendant moieties and pendant moieties having the abilityto form stable enamine structures by reaction with amines and contain adivalent group of the structure ##STR16## wherein R₁ is either H, a C₁to C₁₀ alkyl group, or phenyl, wherein the non-polymeric polyfunctionalamine has at least two amine-functional moieties and wherein the amountof base in the formulation is effective for inhibiting gellation, whichwould otherwise occur as a result of crosslinking to the point ofgellation between the pendant moieties having the ability to form stableenamine structures and amine-functional moieties, thereby producing areaction mixture; holding the reaction mixture at a preselected reactiontemperature for a predetermined period of time, thereby producing theaqueous evaporable polymeric formulation wherein the polymericformulation is stable for at least 12 months at 20° C. and wherein theonly mutually reactive pendant moieties present in the polymericformulation which crosslink are the pendant moieties having the abilityto form stable enamine structures and the amine-functional moieties. 5.The method of claim 4 wherein the polymeric ingredient having thependant moieties having the ability to form stable enamine structures isformed by the reaction of acetoacetoxy ethylmethacrylate and at leastone vinylic monomer which is copolymerizable with acetoacetoxyethylmethacrylate.
 6. The method of claim 4 wherein the pendant moietieshaving the ability to form stable enamine structures present in thepolymeric ingredient are derived from a monomeric ingredient representedby the following structure: ##STR17## wherein R₁ is either H, a C₁ toC₁₀ alkyl group, or phenyl; wherein A is either: ##STR18## wherein R₂ iseither H, a C₁ to C₁₀ alkyl group, phenyl, halo, CO₂ CH₃, or CN;whereinR₃ is either H, a C₁ to C₁₀ alkyl group, phenyl, or halo; wherein R₄ iseither a C₁ to C₁₀ alkylene group or phenylene; wherein R₅ is alkylene;wherein a, m, n, and q are either 0 to 1; wherein X and Y are eacheither --NH-- or --O--; and wherein B is A, a C₁ to C₁₀ alkyl group orphenyl.
 7. The method of claim 4 wherein the base is ammonia or avolatile amine.
 8. The method of claim 6 wherein the monomericingredient is selected from the group consisting of structures of theformula ##STR19## and combinations thereof.
 9. The method of claim 6wherein the monomeric ingredient is selected from the group consistingof acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, allylacetoacetate, vinyl acetoacetate, and combinations thereof.
 10. Themethod of claim 6 wherein the monomeric ingredient is selected from thegroup consisting of acetoacetoxyethyl methacrylate, acetoacetoxyethylacrylate, and combinations thereof.
 11. The method of claim 4 whereinthe acid-functional moieties present in the polymeric ingredientcontaining them are derived from a monomeric ingredient which is anethylenically-unsaturated carboxylic acid moiety-containing monomer. 12.The method of claim 11 wherein the monomeric ingredient is selected fromthe group consisting of acrylic acid, ethacrylic acid, fumaricacid-monoethyl ester, fumaric acid, itaconic acid, maleic acid, maleicanhydride, methacrylic acid, fumaric acid-monomethyl ester, methylhydrogen maleate, and combinations thereof.
 13. The method of claim 11wherein the monomeric ingredient is selected from the group consistingof acrylic acid, methacrylic acid, and combinations thereof.
 14. Themethod of claim 6 wherein the acid-functional moieties present in thepolymeric ingredient containing them are derived from a monomericingredient which is an ethylenically-unsaturated carboxylic acidmoiety-containing monomer.
 15. The method of claim 14 wherein themonomeric ingredient is selected from the group consisting of acrylicacid, ethacrylic acid, fumaric acid-monoethyl ester, fumaric acid,itaconic acid, maleic acid, maleic anhydride, methacrylic acid, fumaricacid-monomethyl ester, methyl hydrogen maleate, and combinationsthereof.
 16. The method of claim 14 wherein the monomeric ingredient isselected from the group consisting of acrylic acid, methacrylic acid,and combinations thereof.
 17. The method of claim 4 wherein the base isammonia or a volatile amine selected from the group consisting of methylamine, dimethyl amine, trimethyl amine, ethyl amine, diethyl amine,triethyl amine, isopropyl amine, dipropyl amine, n-propyl amine, n-butylamine, sec-butyl amine, t-butyl amine, and mixtures thereof.
 18. Themethod of claim 4 wherein the non-polymeric polyfunctional amine has achemical-formula weight of less than about 2,000 grams per mole.
 19. Themethod of claim 4 wherein the evaporable carrier comprises water and atleast one volatile water-miscible liquid organic compound that is ableto evaporate at room temperature, and wherein the total amount ofvolatile organic compound in the formulation does not exceed 200 gramsper liter of the formulation.
 20. The method of claim 4 wherein thenonpolymeric polyfunctional .amine is selected from the group consistingof hexamethylene diamine, 2-methyl pentamethylene diamine, 1,3-diaminopentane, dodecane diamine, 1,2-diamino cyclohexane, 1,4-diaminocyclohexane, para-phenylene diamine, 3-methyl piperidine, isophoronediamine, bis-hexamethylene triamine, diethylene triamine, andcombinations thereof.
 21. The method of claim 4 wherein the nonpolymericpolyfunctional amine is selected from the group consisting ofhexamethylene diamine, diethylene triamine, and combinations thereof.22. The method of claim 14 wherein the base is ammonia or a volatileamine, the non-polymeric polyfunctional amine is selected from the groupconsisting of hexamethylene diamine, 2-methyl pentamethylene diamine,1,3-diamino pentane, dodecane diamine, 1,2-diamino cyclohexane,1,4-diamino cyclohexane, para-phenylene diamine, 3-methyl piperidine,isophorone diamine, bis-hexamethylene triamine, diethylene triamine, andcombinations thereof; the polymeric ingredient has a weight averagemolecular weight of from about 2,000 to about 40,000 and has an acidnumber in the range of about 30 to about
 300. 23. The method of claim 16wherein the base is ammonia or a volatile amine, the non-polymericpolyfunctional amine is selected from the group consisting ofhexamethylene diamine, diethylene triamine, and combinations thereof;the polymeric ingredient has a weight average molecular weight of fromabout 2,000 to about 30,000 and has an acid number in the range of about50 to about
 150. 24. A method of producing a novel aqueous polymericformulation, comprising the steps of:producing a single package aqueousevaporable polymeric formulation that is stable for extended periods oftime by admixing ingredients consisting essentially of at least twopolymeric ingredients, a non-polymeric polyfunctional amine, and base,in an evaporable aqueous carrier, wherein one of the two polymericingredients has acid-functional pendant moieties and the other of thetwo polymeric ingredients has pendant moieties having the ability toform stable enamine structures by reaction with amines and contain adivalent group of the structure ##STR20## wherein R₁ is either H, a C₁to C₁₀ alkyl group, or phenyl, wherein the non-polymeric polyfunctionalamine has at least two amine-functional moieties and wherein the amountof base in the formulation is effective for inhibiting gellation, whichwould otherwise occur as a result of crosslinking to the point ofgellation between the pendant moieties having the ability to form stableenamine structures and amine-functional moieties, thereby producing areaction mixture; holding the reaction mixture at a preselected reactiontemperature for a predetermined period of time, thereby producing theaqueous evaporable polymeric formulation wherein the polymericformulation is stable for at least 12 months at 20° C. and wherein theonly mutually reactive pendant moieties present in the polymericformulation which crosslink are the pendant moieties having the abilityto form stable enamine structures and the amine-functional moieties. 25.The method of claim 24 wherein the polymeric ingredient having thependant moieties having the ability to form stable enamine structures isformed by the reaction of acetoacetoxy ethylmethacrylate and at leastone vinylic monomer which is copolymerizable with acetoacetoxyethylmethacrylate.
 26. The method of claim 24 wherein the pendantmoieties having the ability to form stable enamine structures present inthe polymeric ingredient are derived from a monomeric ingredientrepresented by the following structure: ##STR21## wherein R₁ is eitherH, a C₁ to C₁₀ alkyl group, or phenyl; wherein A is either: ##STR22##wherein R₂ is either H, a C₁ to C₁₀ alkyl group, phenyl, halo, CO₂ CH₃,or CN;wherein R₃ is either H, a C₁ to C₁₀ alkyl group, phenyl, or halo;wherein R₄ is either a C₁ to C₁₀ alkylene group or phenylene; wherein R₅is alkylene; wherein a, m, n, and q are either 0 to 1; wherein X and Yare each either --NH-- or --O--; and wherein B is A, a C₁ to C₁₀ alkylgroup or phenyl.
 27. The method of claim 24 wherein the base is ammoniaor a volatile amine.
 28. The method of claim 26 wherein the monomericingredient is selected from the group consisting of structures of theformula ##STR23## and combinations thereof.
 29. The method of claim 26wherein the monomeric ingredient is selected from the group consistingof acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, allylacetoacetate, vinyl acetoacetate, and combinations thereof.
 30. Themethod of claim 26 wherein the monomeric ingredient is selected from thegroup consisting of acetoacetoxyethyl methacrylate, acetoacetoxyethylacrylate, and combinations thereof.
 31. The method of claim 24 whereinthe acid-functional moieties present in the polymeric ingredientcontaining them are derived from a monomeric ingredient which is anethylenically-unsaturated carboxylic acid moiety-containing monomer. 32.The method of claim 31 wherein the monomeric ingredient is selected fromthe group consisting of acrylic acid, ethacrylic acid, fumaricacid-monoethyl ester, fumaric acid, itaconic acid, maleic acid, maleicanhydride, methacrylic acid, fumaric acid-monomethyl ester, methylhydrogen maleate, and combinations thereof.
 33. The method of claim 31wherein the monomeric ingredient is selected from the group consistingof acrylic acid, methacrylic acid, and combinations thereof.
 34. Themethod of claim 26 wherein the acid-functional moieties present in thepolymeric ingredient containing them are derived from a monomericingredient which is an ethylenically-unsaturated carboxylic acidmoiety-containing monomer.
 35. The method of claim 34 wherein themonomeric ingredient is selected from the group consisting of acrylicacid, ethacrylic acid, fumaric acid-monoethyl ester, fumaric acid,itaconic acid, maleic acid, maleic anhydride, methacrylic acid, fumaricacid-monomethyl ester, methyl hydrogen maleate, and combinationsthereof.
 36. The method of claim 34 wherein the monomeric ingredient isselected from the group consisting of acrylic acid, methacrylic acid,and combinations thereof.
 37. The method of claim 24 wherein thenon-polymeric polyfunctional amine has a chemical-formula weight of lessthan about 2,000 grams per mole.
 38. The method of claim 24 wherein theevaporable carrier comprises water and at least one volatilewater-miscible liquid organic compound that is able to evaporate at roomtemperature, and wherein the total amount of volatile organic compoundin the formulation does not exceed 200 grams per liter of theformulation.
 39. The method of claim 37 wherein the nonpolymericpolyfunctional amine is selected from the group consisting ofhexamethylene diamine, 2-methyl pentamethylene diamine, 1,3-diaminopentane, dodecane diamine, 1,2-diamino cyclohexane, 1,4-diaminocyclohexane, para-phenylene diamine, 3-methyl piperidine, isophoronediamine, bis-hexamethylene triamine, diethylene triamine, andcombinations thereof.
 40. The method of claim 37 wherein thenon-polymeric polyfunctional amine is selected from the group consistingof hexamethylene diamine, diethylene triamine, and combinations thereof.41. The method of claim 34 wherein the base is ammonia or a volatileamine, the non-polymeric polyfunctional amine is selected from the groupconsisting of hexamethylene diamine, 2-methyl pentamethylene diamine,1,3-diamino pentane, dodecane diamine, 1,2-diamino cyclohexane,1,4-diamino cyclohexane, para-phenylene diamine, 3-methyl piperidine,isophorone diamine, bis-hexamethylene triamine, diethylene triamine, andcombinations thereof; the polymeric ingredient having acid-functionalpendant moieties has a weight average molecular weight of from about2,000 to about 40,000 and has an acid number in the range of about 50 toabout 150; and the polymeric ingredient having the pendant moietieshaving the ability to form stable enamine structures has a weightaverage molecular weight of between about 5,000 and about 500,000. 42.The method of claim 36 wherein the base is ammonia or a volatile amine,the non-polymeric polyfunctional amine is selected from the groupconsisting of hexamethylene diamine, diethylene triamine, andcombinations thereof; the polymeric ingredient having acid-functionalpendant moieties has a weight average molecular weight of from about2,000 to about 30,000 and has an acid number in the range of about 50 toabout 150; and the polymeric ingredient having the pendant moietieshaving the ability to form stable enamine structures has a weightaverage molecular weight of between about 50,000 and about 20,000. 43.The method of claim 24 wherein the base is ammonia or a volatile amineselected from the group consisting of methyl amine, dimethyl amine,trimethyl amine, ethyl amine, diethyl amine, triethyl amine, isopropylamine, dipropyl amine, n-propyl amine, n-butyl amine, sec-butyl amine,t-butyl amine, and mixtures thereof.